CN1255486C - Aluminate surface modified microcrystal white mica active filler and its preparation method - Google Patents
Aluminate surface modified microcrystal white mica active filler and its preparation method Download PDFInfo
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- CN1255486C CN1255486C CN 200410040808 CN200410040808A CN1255486C CN 1255486 C CN1255486 C CN 1255486C CN 200410040808 CN200410040808 CN 200410040808 CN 200410040808 A CN200410040808 A CN 200410040808A CN 1255486 C CN1255486 C CN 1255486C
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Abstract
The present invention discloses aluminate ester coupling agent surface modified microcrystal white mica active powdery filler and a preparation method thereof. Microcrystal white mica powder is used as raw material. The preparing technology of the filler comprises: microcrystal white mica powder material is dried under the condition of 110 DEG C or so, and whole adsorption moisture is removed; the aluminate ester is melted at the temperature which is slightly higher than a melting temperature of 70 to 73 DEG C; the material is weighed, dried and put in a high-speed mixer; the material is preheated and stirred at a high speed in the high-speed mixer for 30 min or so, and temperature is controlled to be no more than 73 DEG C; aluminic acid ester is weighed according to the weight ratio to the material and the aluminate ester of 100:0.5 to 3.9; the kinds of material are mixed at a high speed; the aluminate ester is slowly and even poured into the high-speed mixer to be mixed at a high speed for 20 min or so, and temperature is controlled to be no more than 90 DEG C; a modified effect is detected and evaluated by using methods, such as a viscosity test, etc. The filler has the advantages of rich resource, simple modified technology, low cost, good effect and wide purpose and has obvious economic and social benefit.
Description
One, technical field
The present invention relates to active powder filler of microcrystal muscovite of a kind of aluminate coupling agent surface modification and preparation method thereof, applicable to plastics, rubber, coating, industry such as tackiness agent, especially be suitable as PVC (polyvinyl chloride), ABS (acrylonitrile-butadiene-styrene copolymer), PS (polystyrene), PV (polyethylene), PP (polypropylene), the active filler of PE polymkeric substance such as (polyethylene), and can give or improve the chemical stability of institute's filled high polymer material or polymer matrix composite, acid and alkali-resistance, thermotolerance, antiultraviolet, anti-aging, function and character such as infrared rays obstruct are for example at antifouling paint and coating, anti-soda acid pipeline, infrared rays intercepts the effect of middle performance functionally active fillers such as plastic greenhouse film.
Two, technical background
1, white mica and Application Areas thereof
White mica (Muscovite) is the important member of mica family, white mica subtribe mineral, is 2: 1 type dioctahedron layered struture silicate mineralss of a kind of rich K, Al.The ideal composition formula of white mica is: K{Al
2[AlSi
3010] (OH)
2, its Chemical Composition is: K
2O 11.8%, Al
2O
338.5%, SiO
245.2%, H
2O 4.5%.The white mica isomorph substitutes more extensive, therefore has mutation such as roscoelite, fuchsite, phengite.Si: Al in four coordinations of phengite＞3: 1, six coordinate Al are by more Mg and Fe
2+Replace.In addition, so-called sericite generally is meant some very tiny white micas (the normally white mica or the mica of receiving).
White mica has 1Md (unordered type), 1M, 2M
1Many types of with 3T etc., the white mica majority of nature output is 2M
1Type.The white mica crystalline form forms false hexagon or rhombus outward usually in the form of sheets or tabular, sees that sometimes the white mica single crystal is the taper cylinder.The tiny person of crystal is flakey, and big person has hundreds of square centimeters, and maximum can reach 2000cm
2
White mica has many good physical and chemical performances.At first, has very outstanding electrical properties.It is good that it mainly shows as electrical insulating property, is the desirable feedstock of producing the premium insulation material.Secondly, have good thermotolerance, in the time of 100～600 ℃, can keep its a series of good physical.The 3rd, have excellent elasticity and wear resistance, its wear resisting property is better than copper.The 4th, have good chemical stability.Alkali works hardly to white mica, does not dissolve in hot acid, but can decompose under boiling vitriolic long duration of action.The 5th, have the premium properties that shielding ultraviolet rays, counter infrared ray radiation etc. resist various x radiation xs.The 6th, have excellent waterproofness.The white mica water absorbability is 0～0.37%, and water-absorbent is 0～0.23%, is the damp-proof material of excellent waterproof.
The above-mentioned physical and chemical performance of white mica makes it to have purposes very widely.White mica industrial application and its wafer size and crystal chemistry feature have relation nearly.Large stretch of white mica (useful area 24cm
2The person) is mainly used in hard-core technology fields such as electrical industry, electronic industry and Aeronautics and Astronautics.
On the other hand, along with the finiteness of scientific-technical progress and big mica splitting resource is obvious day by day, the Application and Development of garrulous mica (waste material and the natural little mica splitting that comprise fragment mica, big mica splitting processing) has obtained remarkable progress.At first, the mica powder of super-fine processing can be used as the good filler of plastics.White mica powder is easy to mix with Plastic Resin behind surface actives such as coupling agent, and processing characteristics is good, can be used for filling multiple plastics such as PE, PP, PVC, PA, PET, ABS, and can improve the modulus of plastic substrate, improves dielectric properties.Simultaneously, white mica powder has bidimensional enhancing property, can improve thermotolerance, reduces creep, prevents the goods warpage, reduces molding shrinkage.In addition, white mica powder also has the excellent electric insulating energy, and the processing units wearing and tearing are few, and heat-drawn wire improves, the flammable reduction, and perviousness reduces and advantages such as weather-resistant and acid-alkali-corrosive-resisting.The matrix material that obtains with mica enhancing PP/EPDM co-mixing system not only has good impact property but also have higher modulus in flexure, has been widely used in injection moulding hardness fascia and other plastic automotive parts.The second, the mica powder of super-fine processing also is the good filler of rubber and paint, multiple coating.Add mica powder in the rubber, can make the tubeless rubber tire.Add ultra-fine mica powder in the paint and can improve Chinese People's Anti-Japanese Military and Political College's gas, frost resistance, preservative property, closely knit wear resistance, can reduce perviousness, reduce paint film yellowing and be full of cracks.Mix the mica ultrafine powder in the coating and can improve the weather resistance of building appearance, increase water-repellancy, elasticity, plasticity, adhesivity and the non-corrosibility of coating.The 3rd, hot pressing moulding or injection molding are mica ceramics behind mica powder and the glass powder mixing.Mechanical workouts such as this pottery can bore, mill can prepare the special-shaped products complex-shaped, that dimensional precision is high and instrument skeleton plug connector elements and thyristor shell etc.The 4th, the mica paper with fragment mica and mica powder are made all is gradually improved aspect quality and variety, has replaced natural flaky shape mica in a large number, and extensive use is arranged.Pull with mica paper very extensive as mica ply of paper pressure in the industrial application of Electrical and Electronic.Replace the natural flaky mica in a large number although should be pointed out that mica paper, the large stretch of white mica of high-quality does not still have substitute material in sophisticated technology Application for Field such as robot calculator, radar, guided missile, man-made satellites.
2, microcrystal muscovite and application prospect thereof
Microcrystal muscovite (Microcrystal muscovite) is a newcomer of mica family, white mica subtribe mineral, is a kind of novel non-metallic minerals resource.The crystalline structure of microcrystal muscovite, crystal chemistry, Chemical Composition, crystal habit and mineral physics feature of being showed thereof etc. are all identical with white mica or basic identical, thereby should have the physical and chemical performance identical or similar with white mica.With white mica very inequality be, the mineral crystal of microcrystal muscovite is very little, only has micron-sized crystal or wafer (be called for short " crystallite "), its size is generally at 1～10 micron.The origin of title that Here it is " microcrystal muscovite ".
Formation and its origin cause of formation of microcrystal muscovite this distinctive " crystallite " structure have substantial connection.1997, the super-huge microcrystal muscovite mineral deposit of at first being found in somewhere, China Sichuan by the author was exactly typical example.This mineral deposit is to be formed through diagenesis or later hydrothermal alteration transformation by dignified limestone, and large stretch of white mica of known various uses is mainly derived from the granitic pegmatite-type mineral deposit.In the world, except that near Nevada, USA Luo Qisite, found in 1933 with similar agalmatolite ore deposit, this mineral deposit, do not find the report in other place of production so far.Thereby this mineral deposit is the domestic new mica group genetic type of ore deposit of finding first, also is a kind of novel non-metallic minerals resource.According to three mining areas estimations tentatively carrying out at present geological work, the microcrystal muscovite mineral deposits in this mineral deposit add up to * and * * ten thousand tons, it is rare that its scale also belongs to domestic and international institute.
The physical and chemical performance of mineral is must reflecting of mineral self crystalline structure, crystal chemistry.As mentioned above, because features such as the crystalline structure of microcrystal muscovite and crystal chemistry are all basic identical with white mica, thereby it also should have the very good physical and chemical performance identical or similar with white mica,, chemically stable big comprising: resistivity height, physical strength, acid and alkali-resistance, wear resistance, thermotolerance, weathering resistance, antiultraviolet, anti-aging, full of elasticity etc.Simultaneously, microcrystal muscovite removes also has characteristics such as natural superfine, whiteness height, frangible easy mill processing, is easy to be processed into varigrained microcrystal muscovite superfine powdery material.We know that toughness is big, wear resistance is the good physical and chemical performance that white mica has well.Therefore, adopt the difficulty of white mica or garrulous mica processing mica powder and ultra-fine mica powder big, cost is high, restricted its widespread use as functional stuffing.In addition, microcrystal muscovite also has the bigger characteristics of radius-thickness ratio, has tangible strengthening action as rubber filling.In a word, the microcrystal muscovite excellent property, aboundresources is easy to exploitation, and low processing cost has the incomparable advantage of other white non-metallic minerals filler in many industrial application.
This shows, microcrystal muscovite is the good raw mineral materials of preparation mica powder and ultra-fine mica powder, at industrial sectors such as plastics, rubber, electric, electronics, space flight, aviation, automobiles very wide application prospect will be arranged by the functional stuffing of its preparation, and might in Application Areass such as automobile engineering plastics, anti-soda acid plastics, anticorrosive coating and High Performance Insulation material, exhibit one's skill to the full as functional stuffing.And along with the minimizing day by day of large stretch of white mica mineral wealth and the restriction of broken white mica super-fine processing cost, the searching of natural microcrystal muscovite mineral wealth will seem with development and use and become more and more important.
3, the technical problem underlying of microcrystal muscovite in polymer materials is used
In industry such as modern macromolecular material such as plastics, rubber, tackiness agent, polymer matrix composite and functional materials, inorganic nonmetal mineral fillers is occupied very consequence.These inorganic nonmetal mineral fillers, as lime carbonate, kaolin, wollastonite, talcum, mica, pyrophyllite, rhombspar, the tremolite etc., not only can reduce the cost of macromolecular material, superpolymer based composites, and can also improve rigidity, hardness, the dimensional stability of material, and give material some special physicochemical performance, as erosion resistance, flame retardant resistance, insulativity etc.But, because these inorganic nonmetal mineral fillers are different with the interfacial property of polymer matrix material, consistency is poor, in body material, be difficult to disperse, directly or in a large number fill some degradation that often causes material easily.Therefore, for the non-metallic minerals filler, except carrying out processing treatment such as the broken or superfine grinding of fine powder, also must carry out surface modification, make it have surfactivity, to improve the consistency of it and polymeric matrix it, thereby improve the dispersiveness of non-metallic minerals filler in body material, improve the over-all propertieies such as physical strength of composite material interface bonding force and material, and increase the loading level of non-metallic minerals filler, reduce cost.
Modern macromolecular materials such as plastics, rubber, tackiness agent and polymer matrix composite will be the of paramount importance Application Areass of microcrystal muscovite filler.Because natural microcrystal muscovite is the hydrophilic mineral of a kind of polarity, and organic polymers such as plastics, rubber have nonpolar hydrophobic surface.Therefore, if they are directly lumped together, polarity difference each other then, consistency is poor, is difficult to mutual homodisperse, thereby causes the boundary defect of two phase materials, the organic polymer material property is descended or fills restricted greatly.If will make microcrystal muscovite in above-mentioned polymer materials, bring into play the effect of function powder material, must at first carry out the microcrystal muscovite Research on Surface Modification, solve the surface bonding problem of microcrystal muscovite filler and polymer matrix material, give microcrystal muscovite powder filler due surfactivity, to improve its application performance.But because microcrystal muscovite is a kind of novel metalloid raw mineral materials of just finding in recent years, research also is in blank about the micro crystal isinglass active filler process for modifying surface, thereby restricts its industrial application.
In sum, microcrystal muscovite is a kind of novel non-metallic minerals resource, have tangible quality price than advantage as feedstock production mica powder and ultra-fine mica powder,, wide application prospect will be arranged if can adopt process for modifying surface to improve the consistency of it and polymeric matrix.By retrieval, do not find with the microcrystal muscovite to be raw material, the patent application or the bibliographical information of the active powder filler of preparation aluminate coupling agent surface modification of microcrystalline white mica.
Three, summary of the invention
The objective of the invention is, according to microcrystal muscovite and industrial application characteristics thereof, carry out the research of aluminate coupling agent process for modifying surface, develop the active powder filler of a kind of aluminic acid ester surface modification of microcrystalline white mica, applicable to plastics, rubber, coating, industry such as tackiness agent, especially be suitable as PVC (polyvinyl chloride), ABS (acrylonitrile-butadiene-styrene copolymer), PS (polystyrene), PV (polyethylene), PP (polypropylene), the active filler of PE polymkeric substance such as (polyethylene), and can give or improve the chemical stability of institute's filled high polymer material or polymer matrix composite, acid and alkali-resistance, thermotolerance, antiultraviolet, anti-aging, function and character such as infrared rays obstruct are for example at antifouling paint and coating, anti-soda acid pipeline, infrared rays intercepts the effect of middle performance functionally active fillers such as plastic greenhouse film.For this reason, the present invention has adopted following technical scheme:
At present, the method that is used for the non-metallic minerals stuffing surface modification mainly contains surface chemistry coating modification method, mechanochemical modification method and high energy modification method etc.
Surface chemistry coating modification method is present the most frequently used surface modifying method, and it is a kind ofly to utilize the functional group in the organic molecule filler particles surface to be coated the method that it is organised in filling surface absorption or chemical reaction.For this method, the selection of chemical modifier has conclusive effect to the modification result, and the consumption of chemical modifier, modified technique also are the keys that influences modified effect.Present chemical modifier has tensio-active agent and coupling agent two big classes, and modified effect is preferably the coupling agent that can play molecule bridge coupled action on non-metallic minerals filler and organic materials interface.
According to microcrystal muscovite and industrial application characteristics thereof, the method that this patent adopted is a surface chemistry coating modification method, and chemical modifier is a coupling agent.Putting before this, the related gordian technique of the art of this patent scheme has: the definite and consumption of (1) coupling agent; (2) the coupling agent thinner determines and consumption; (3) surface modification technology etc.
1, coupling agent determines and consumption
Coupling agent is a kind of surface-modifying agent most widely used, with fastest developing speed in the non-metallic minerals stuffing surface modification, various in style, the type complexity mainly contains series product such as silane, titanic acid ester, aluminic acid ester, zircoaluminate, organic complex, phosphoric acid ester, boric acid ester, stannic acid ester, aluminium titanium composite coupler.Wherein, it is more that first three plants serial kind, uses also the widest.
The selection of coupling agent except that the modified effect of considering coupling agent itself, also will be considered industrial application and Financial cost and composite factor such as easy to operate.In three big serial coupling agents such as widely used silane, titanic acid ester, aluminic acid ester, the most cheap with the aluminic acid ester, and also its surface modification effect can match in excellence or beauty with titanate coupling agent.Aluminate coupling agent all has coupling effect preferably to many polymkeric substance, and it can improve the goods physical and mechanical properties when improving filled plastics goods processing characteristics, as improve shock strength, improve heat-drawn wire, and coloured shallow, nontoxic, easy to use, characteristics such as Heat stability is good.The major industry Application Areas of considering this product simultaneously is the filler with chemically stable, acid and alkali-resistance, thermotolerance, antiultraviolet, macromolecular material such as anti-aging or polymer matrix composite, and this patent has been selected aluminate coupling agent.
Aluminate coupling agent is a kind of novel coupling agent by inventions such as Fujian China normal university chapter literary composition tributes.Its chemical general formula is: (C
3H
7O) xAl (OCOR) m (OCORCOOR) n (OAB) y, x+m+n=3 wherein, y=0～2.At present, the following series product of aluminate coupling agent:
(1) the cured shape solid of oyster white: 70～73 ℃ of its melting ranges comprise the DL-411-A of Semi-polarity composite plastic products such as being applicable to PVC, PS, ABS, PV, DL-411-AF; Be applicable to the DL-411-D of low polarity composite plastic products such as PP, PE, DL-411-DF.
(2) weak yellow liquid: comprise DL-411, DL-411-B, DL-411-C, DL-451-A.
The described aluminate coupling agent of this patent is comprise above-mentioned series products present by the different trades mark of relevant enterprise production and the aluminate coupling agent of title.
In the structure of aluminate coupling agent, the aluminium radius is little, and the charge number height has good affinity to mineral filler.Long-chain hydrocarbon R, carbon atom number generally between 14～22, have affinity and winding effect to macromolecular material, and give the material certain toughness.Hydrocarbon short chain A, B, carbon atom number can promote that thing improves Drawing abillity between 6～8.The molecular weight of such coupling agent generally is controlled at 1000～2000, and molecular weight is too big, mineral filler effect difficulty; Too little, coupling agent molecule and macromolecular material consistency are poor.
Aluminate coupling agent is handled applicable to the activation modification of various polarity filler and material surface, many polymkeric substance all there is coupling effect preferably, the also available Chemical bond theory of its mechanism of action is explained: the functional group that exists two kinds of character in the structure of aluminate coupling agent, a kind of functional group can react in the polar group on inorganics surface, another kind of functional group then can react with organism, based on this coupling agent both is combined with chemical force.The monoalkoxy of aluminate coupling agent can react with the hydroxyl hydrogen atom on the filling surface, forms chemical bond; Other two organic long-chains can twine with polymer molecule.So just polymkeric substance and mineral filler are closely combined.
In addition, the loading level in polymer materials is more greatly an important feature of the active powder filler of aluminic acid ester surface modification.Its major cause is: aluminate coupling agent is a unimolecular layer filling surface formation, thereby can obtain good dispersiveness, wettability and coupling efficiency, and can prevent that the viscosity of infill system from increasing, keep good flowability, can realize high fillingization like this.
For some coupling agent, can calculate its theoretical consumption W (g) by following formula:
W=(W
1* S
1)/S
2(formula 1)
In the formula: W
1---desire the mineral filler weight (g) of modification;
S
1---the specific surface area (m of mineral filler
2/ g);
S
2---the minimum of coupling agent coats area (m
2/ g), can provide data with reference to manufacturer.
But what calculated by above-mentioned formula is theoretical consumption.During practical application, because crystal chemistry, crystal habit, granular size and the surface characteristic etc. of different non-metallic minerals fillers all have bigger difference, so theoretical consumption and actual amount also have than big difference.The coupling agent actual amount is generally the 0.5-3% of mineral weight.In general, mineral granularity is thin more, and specific surface area is big more, and the consumption of required properties-correcting agent is big more.Therefore, this patent determines that the method for coupling agent consumption is: calculate the theoretical consumption of different grain size microcrystal muscovite filler earlier by above-mentioned formula, observation and test analysis are verified and are revised by experiment again, sift out optimum amount at last.The aluminate coupling agent consumption of different grain size microcrystal muscovite will provide in the specific examples of this patent.
2, thinner determines and consumption
Generally, coupling agent is very important with solvent cut, and it can make coupling agent evenly be coated on the surface of microcrystal muscovite filler.The thinner that can be used as aluminate coupling agent has organic reagents such as white oil, ethanol, acetone, toluene.
But this patent is by adding white oil or acetone diluted agent and the surface modification effect contrast experiment who does not add any thinner, and the result shows: for aluminate coupling agent, the effect of thinner is also not obvious.On the contrary, add thinner and not only can increase the modification cost, and environment is had certain pollution.Therefore, this patent adopts the technical scheme of not adding any thinner.
3, surface modification technology
The technology approach of surface chemistry coating modification method has two kinds: (1) method for pretreating: earlier filler is carried out surface modification treatment, be added to then and remove to form matrix material in the base-material; (2) whole blending method:, after forming process, form matrix material in that filler and polymkeric substance are added surface-modifying agent when mixing.In general, the modified effect of method for pretreating is better than whole blending method.In order to help producing, this patent has adopted the method for pretreating modified technique.
The method for pretreating modified technique also has two kinds of methods: a kind of is dry method, after promptly coupling agent being handled with solvent cut etc., joins in the powder material, then high-speed stirring (being no more than 90 ℃ usually, about stirring velocity 2000r/min).Dry method does not need dewatered drying, operates more conveniently, and production cost is lower, but manufacturing technique requirent is relatively stricter, otherwise easily mixes inhomogeneous and influence quality.A kind of is wet method, is about to coupling agent and is mixed with dilute solution by 1～3% of powder material weight, makes powder material fully effect in solution, dries then, encapsulates.Wet method is applicable to water-soluble coupling agent, and modification ratio is relatively more even, but power consumption is bigger in the industrial production, and production cost is higher.This patent purpose is to be enterprises service, the method for modifying that should select a kind of suitable enterprise to produce, and simultaneously according to the aluminate coupling agent characteristics, this patent has adopted dry process.
This patent adopts the temperature controllable high-speed mixer that microcrystal muscovite powder material is carried out surface modification, and its specific embodiment (dry method) is:
(1) oven dry material: microcrystal muscovite powder material is dried under 110 ℃ of left and right sides constant temperatures, remove whole adsorption moistures in the material.It is definite that drying time should be done wet situation according to material, generally about 3 hours;
(2) melting aluminum acid esters:, should under a little more than its melting temperature (70～73 ℃), the aluminic acid ester be melted for cured shape solid aluminium acid esters.For preventing that the aluminic acid ester from solidifying, should be under the temperature condition about 70 ℃ that its preservation is standby.
(3) take by weighing material; Take by weighing the microcrystal muscovite powder oven dry material of certainweight, certain particle size, in the modified device temperature controllable high-speed mixer of packing into, and fasten the high-speed mixer sealing cover by the operational requirement of this equipment;
(4) pre-thermal material: open the high-speed mixer switch, high-speed stirring made the preheating of microcrystal muscovite powder material about 30 minutes, controlled temperature≤73 ℃;
(5) take by weighing the aluminic acid ester: weight is in microcrystal muscovite powder material: the ratio of aluminic acid ester=100: 0.5～3.9 claims (amount) to get aluminate coupling agent;
(6) high-speed mixing material: slowly, evenly pour into aluminate coupling agent in the high-speed mixer that microcrystal muscovite powder material is housed; Then, about high-speed mixing 20min, temperature is controlled at≤90 ℃ (when microcrystal muscovite powder material more after a little while, can take to pour at twice aluminate coupling agent, the time of pouring into for the second time is at total mixing time one half).By the time after setting mixing time, take out material, promptly obtain the active powder filler of aluminic acid ester surface modification of microcrystalline white mica by operational requirement;
(7) modified effect detects: microcrystal muscovite powder material is after the aluminate coupling agent surface modification, and its table picture character will become " oleophilic drainage " by " hydrophilic oleophobic ".Active powder after the surface modification will float on the water surface, be difficult for submerged.In view of the above, can adopt simple and easy method to carry out modified effect at the scene observes and estimates.Simultaneously, can adopt methods such as activation index analysis, viscosity test, nephelometric analysis and Infrared spectroscopy, surface modification effect is done further detection and evaluation.
4, surface modification effect characterizes and estimates
The characterizing method of non-metallic minerals stuffing surface modification effect has two kinds of direct method and indirect methods.Direct method is powder filled in corresponding plastics, rubber, coating, tackiness agent with after the surface modification, and the physical and chemical performance of the polymer matrix composite after filling by test analysis is estimated modified effect.Indirect method is to estimate by the correlated performance of test analysis modified powder itself.Because the industrial application of the active powder filler of aluminic acid ester surface modification of microcrystalline white mica is wider, can not directly verifies one by one with regard to various uses, thereby adopt indirect method to carry out the surface modification effect sign.
According to the characteristics of the active powder filler of aluminic acid ester surface modification of microcrystalline white mica, this patent adopts methods such as activation index analysis, viscosimetric analysis, nephelometric analysis and Infrared spectroscopy to characterize and estimate.
(1) simple on-site is observed
Take by weighing active powder filler 2 grams of microcrystal muscovite after the surface modification, put into the beaker of 50 ml distilled waters, the active powder filler of microcrystal muscovite will swim in the water surface immediately, does not almost have powder.On the contrary, take by weighing the unmodified microcrystal muscovite powder of 2 grams, put into the beaker that fills 50 ml distilled waters, will very fast whole submergeds, almost there is not floating matter.Hence one can see that, and whether the active powder filler of the aluminic acid ester surface modification of microcrystalline white mica after the modification has become " lipophilicity " by " wetting ability ", whether has reached surface modification effect.
(2) activation index analysis
The general relative density of mineral filler powder is bigger, and the surface is polarization state, and nature can sink in water.The reason that produces above hydro-planing is, the active powder filler of the microcrystal muscovite after surface modification treatment, and the surface is become nonpolar by polarity, water is presented more intense non-infiltration.The fine particle of this non-infiltration because huge surface tension makes it floating not heavy as oil film, has had activation index H thus in water:
Without the inorganic powder that the surface active modification is handled, H=0; When activation treatment is the most thorough, H=1.0.According to the changing conditions of activation index H=0～1.0, can detect and estimate surface modification effect.The experimental result of this patent shows that adopting the activation index analysis is a kind of effective and rapid method that detects the active powder filler of aluminic acid ester surface modification of microcrystalline white mica effect.
(3) viscosimetric analysis
Adopt viscosity tester, measure aluminic acid ester surface modified micro crystal isinglass active filler through different amounts in mineral oil medium viscosity value, to determine the optimum amount of aluminic acid ester.The experimental result of this patent shows that adopting viscosimetric analysis is to determine and sign aluminate coupling agent optimum amount, detection and evaluation surface modification effect most effectual way.
(4) nephelometric analysis
Nephelometric analysis is to utilize the dispersion effect of powder filler in whiteruss to estimate a kind of quantificational expression method of the dispersing property of powder filler in nonpolar medium.Nephelometric analysis can calculate with following formula.
The transmittance of the transmittance-suspension of turbidity=liquid juice paraffin (formula 3)
By formula 3 as can be known, the turbidity of dispersion system is suspended in whiteruss by powder granule and causes, the turbidity in arbitrary moment of dispersion system is by all particulate volume decisions that suspend in the liquid, the suspension time of particle in liquid is long, powder can form stable dispersion system at liquid, then the turbidity of dispersion system is big, otherwise then turbidity is little.Therefore, the solid-liquid interface that big explanation particle of turbidity and liquid form is stable, and the avidity of solid-liquid interface is strong, is difficult between the particle reuniting, and powder stably disperses in liquid easily, and dispersion system is a heating power stabilising system; A little less than the avidity of the bright solid-liquid interface of turbidity novel, reunite easily between the particle and sink at the bottom of the turbidity cup, powder can not form stable dispersion system in liquid.
(5) Infrared spectroscopy
The variation characteristic of the infrared spectra collection of illustrative plates of microcrystal muscovite powder before and after the surface modification, the situation that combines that can reflect coupling agent and microcrystal muscovite powder, as: whether coupling agent is coated on the microcrystal muscovite powder, have or not new chemical bond formation etc., can understand and estimate the effect of microcrystal muscovite stuffing surface modification thus.
5, technical superiority
Compared with prior art, this patent modified effect is good, and is with low cost, and technology is convenient, and its end-use is extensive, can produce tangible economy and society benefit.The technical superiority of this patent is embodied in:
(1) modified effect is good.The microcrystal muscovite filler of long time without surface modification is a kind of polarity inorganics, has " hydrophilic oleophobic " surface characteristic, relatively poor with the affinity of organic polymer matrix, directly filling cause easily in machine superpolymer base-material, disperse inhomogeneous, thereby cause the boundary defect of two phase materials.The modified effect detected result shows, aluminic acid ester surface modified micro crystal isinglass active filler has " oleophilic drainage " surface characteristic, demonstration is good with the affinity of organic polymer matrix, can be filled in the organic polymer base-material by homodisperse the effect of performance function powder filler.
(2) modification is with low cost.In three big serial coupling agents such as widely used silane, titanic acid ester, aluminic acid ester, the aluminic acid ester is the most cheap, and its price only is 1/2～1/3 of a titanate coupling agent, and its surface modification effect can match in excellence or beauty with titanate coupling agent.This patent adopts temperature controllable high-speed mixer dry modification process, and equipment is simple, low price, and production cost is low, helps on price with other white non-metallic minerals filler and surface modified product competition thereof.
(3) modified technique is convenient.As mentioned above, the temperature controllable high-speed mixer dry method modification method that this patent adopted, technical process is simple, and the mechanization degree height is easy to operate, is suitable for large-scale mass production.
(4) modified product is of many uses.Aluminate coupling agent is handled applicable to the activation modification of various polarity filler and material surface, and many polymkeric substance are all had coupling effect preferably.The active powder filler of the microcrystal muscovite of aluminate coupling agent surface modification is applicable to industry such as plastics, rubber, coating, tackiness agent, especially be suitable as have chemically stable, the active function filler of PVC (polyvinyl chloride), the ABS (acrylonitrile-butadiene-styrene copolymer) of functions such as acid and alkali-resistance, thermotolerance, antiultraviolet, anti-aging, infrared rays obstruct, PS (polystyrene), PV (polyethylene), PP (polypropylene), PE polymkeric substance such as (polyethylene).
(5) economic benefit is obvious.This patent technology is convenient, and low production cost can obviously improve the physical and chemical performance of microcrystal muscovite filler, widens its industrial application, and makes its increment; Simultaneously, the dispersiveness of the active powder filler of aluminic acid ester surface modification that this patent is prepared and mobile fine has big loading level in polymer materials, when improving institute's filled polymer material correlated performance, can reduce the respective material production cost.Thereby this patent can produce tangible economy and society benefit.
Four, description of drawings
Accompanying drawing 1: the X-ray powder crystal diffraction analysis (XRD) of somewhere, Sichuan microcrystalline white mica powder (600 order) (laboratory apparatus: Japanese Rotaflex D/max C type x x ray diffractometer x of science; Experiment condition: CuK α radiation, the filtering of Ni sheet, operating voltage 35KV, electric current are 25mA, sweep velocity is 4deg/min);
Accompanying drawing 2: the infrared absorpting light spectra (IR) of somewhere, Sichuan microcrystalline white mica powder (600 order) (laboratory apparatus: the Spectrum On of U.S. PE company down together);
Accompanying drawing 3: the infrared absorpting light spectra (IR) of aluminic acid ester DL-411-D;
Accompanying drawing 4: the infrared absorpting light spectra of aluminic acid ester DL-411-D surface modified micro crystal isinglass active filler (600 orders, consumption are 1.2%).
Five, embodiment
Example 1:
Micro crystal isinglass active filler of aluminic acid ester surface modification (600 order) and preparation method thereof.The microcrystal muscovite powder sample that this example adopted originates from super-huge microcrystal muscovite mineral deposit, somewhere, Sichuan.As mentioned above, this mineral deposit is at first found in 1997 by applicant Chengdu University of Technology.In the past few years, Sichuan Xinju Mineral Resource Development Co., Ltd and the scientific and technical personnel of Chengdu University of Technology have done certain work with regard to aspects such as Sichuan microcrystal muscovite ore type, chemical ingredients, mineralogical composition, structure construction and ore dressing experiments, and have succeeded in developing varigrained prosperous torch board microcrystal muscovite powder product series such as 200 orders, 325 orders, 400 orders, 600 orders, 800 orders, 1250 orders and 2500 orders in view of the above.The varigrained microcrystal muscovite sample of all examples of this patent is all taken from the prosperous torch board microcrystalline white mica powder of institute of Sichuan Xinju Mineral Resource Development Co., Ltd process for processing, and its Chemical Composition and physical and chemical performance are as shown in Table 1 and Table 2.
The chemical ingredients (%) of table somewhere, l Sichuan microcrystalline white mica powder
| SiO 2 | Al 2O 3 | K 2O | Fe 2O 3 | MgO | Na 2O | CaO | TiO 2 | MnO | P 2O 5 |
| 45.7 | 30.51 | 11.63 | 2.50 | 1.65 | 0.12 | 0.59 | 0.07 | 0.09 | 0.03 |
Annotate: this table draws the product description from Sichuan Xinju Mineral Resource Development Co., Ltd
The physical and chemical performance of somewhere, table 2 Sichuan microcrystalline white mica powder
Annotate: this table draws the product description from Sichuan Xinju Mineral Resource Development Co., Ltd
The author adopts X-ray powder crystal diffraction analysis (XRD, accompanying drawing 1), infrared absorption spectrum (IR, accompanying drawing 2), heat to analyze (DTA-TG) and transmission electron microscope technological methods such as (SEM), and the microcrystalline white mica powder sample used to this example carried out test analysis.The result shows that prosperous torch board microcrystalline white mica powder mainly is made up of microcrystal muscovite, and its content is more than 90%, and contains a small amount of konilite mineral; The mineral of microcrystal muscovite are many types of to be 2M
l, its crystal in the form of sheets or lamellar, wafer size is generally less than 10 μ m, variation range l μ m～18 μ m, average out to 4 μ m, radius-thickness ratio has typical " crystallite " feature more than 20.
This patent is the aluminic acid ester DL-411-D that Fujian teacher normal university polymer Research Institute is produced to the aluminate coupling agent that example adopted.Its infrared absorption spectrum analysis (IR, accompanying drawing 3) result shows that its feature is identical with the standard spectrogram.
This example adopts the temperature controllable high-speed mixer that microcrystal muscovite powder material (600 order) is carried out surface modification, and its technological process is (dry method):
(1) oven dry material: microcrystal muscovite powder material is dried under 110 ℃ of left and right sides constant temperatures, remove whole adsorption moistures in the material.It is definite that drying time should be done wet situation according to material, generally about 3 hours;
(2) melting aluminum acid esters:, should under a little more than its melting temperature (70～73 ℃), the aluminic acid ester be melted for cured shape solid aluminium acid esters.For preventing that the aluminic acid ester from solidifying, should be under the temperature condition about 70 ℃ that its preservation is standby;
(3) take by weighing material: take by weighing the microcrystal muscovite powder oven dry material of certainweight, certain particle size, in the modified device temperature controllable high-speed mixer of packing into, and fasten the high-speed mixer sealing cover by the operational requirement of this equipment;
(4) pre-thermal material: open the high-speed mixer switch, high-speed stirring made the preheating of microcrystal muscovite powder material about 30 minutes, controlled temperature≤73 ℃;
(5) take by weighing the aluminic acid ester: weight is in microcrystal muscovite powder material: the ratio of aluminic acid ester=100: 1.20 claims (amount) to get aluminate coupling agent.The aluminic acid ester amount ranges (wt%) of the used granularity microcrystal muscovite of this example powder is as shown in table 3;
(6) high-speed mixing material: slowly, evenly pour into aluminate coupling agent in the high-speed mixer that microcrystal muscovite powder material is housed; Then, about high-speed mixing 20min, controlled temperature≤90 ℃ (when microcrystal muscovite powder material more after a little while, can take to pour at twice aluminate coupling agent, the time of pouring into for the second time is at total mixing time one half).By the time after setting mixing time, take out material, promptly obtain the active powder filler of aluminic acid ester surface modification of microcrystalline white mica by operational requirement;
(7) modified effect detects: microcrystal muscovite powder material is after the aluminate coupling agent surface modification, and its surface properties will become " oleophilic drainage " by " hydrophilic oleophobic ".Active powder after the surface modification will float on the water surface, be difficult for submerged.In view of the above, can adopt simple and easy method to carry out modified effect at the scene observes and estimates.Simultaneously, can adopt methods such as activation index analysis, viscosity test, nephelometric analysis and Infrared spectroscopy, surface modification effect is done further detection and evaluation.
The consumption (wt%) of table 3 aluminate coupling agent DL-411-D in different grain size microcrystal muscovite stuffing surface modification
| Microcrystal muscovite granularity (order) | 200 | 325 | 600 | 800 | 1250 | 2500 |
| Specific surface area (cm 2/cm 3) *Aerated density (g/cm 3) *Theoretical consumption (wt%) aluminic acid of aluminic acid ester ester test consumption (wt%) aluminic acid ester amount ranges (wt%) | 6000 0.36 0.52 0.50 0.50～0.55 | 8000 0.24 1.04 1.00 1.00～1.05 | 10000 0.25 1.25 1.20 1.20～1.25 | 12000 0.23 1.63 1.50 1.50～1.65 | 21000 0.22 2.98 2.80 2.80～3.00 | 25860 0.20 4.04 3.90 3.90～4.05 |
Annotate:
*Data are drawn from Sichuan Xinju Mineral Resource Development Co., Ltd's product description (table 2); The theoretical consumption (wt%) of aluminic acid ester DL-411 one D is by theoretical formula
(1) consumption that directly calculates.The minimum of aluminic acid ester DL-411-D coats area S
2Be 320m
2/ g (providing) by manufacturer.
Activation index analysis, viscosity test and nephelometric analysis result show, adopt a kind of aluminic acid ester surface modified micro crystal isinglass active filler (600 order) of above processing method preparation to reach surface modification effect preferably.Accompanying drawing 4 is that the aluminate coupling agent consumption is the infrared absorpting light spectra of the active powder filler of 1.20% surface modification of microcrystalline white mica (600 order), at 2959.6cm
-1, 2921.5cm
-1And 2852.1cm
-1Deng there being tangible aluminic acid ester absorption peak to produce on the position, show aluminate coupling agent in some way with microcrystal muscovite powder material generation coupling activation.
Example 2:
Micro crystal isinglass active filler of aluminic acid ester surface modification (200 order) and preparation method thereof.The features such as the place of production, mineral composition, Chemical Composition and mineral physics of the microcrystal muscovite filler that this example adopted (200 order) are all identical with this patent example 1; Its Chemical Composition and physical and chemical performance are as shown in Table 1 and Table 2.
The aluminate coupling agent DL-411-D that this example adopted is identical with this patent example 1; Its surface modification technology is also identical with this patent example 1, as shown in table 3, this example coupling agent weight that different is is by microcrystal muscovite powder material: aluminic acid ester=100: 0.50, the aluminic acid ester amount ranges (wt%) of the used granularity microcrystal muscovite of this example powder is as shown in table 3.
This example adopts and example 1 same procedure, and surface modification effect is characterized and estimates, and shows that the coupling activation is respond well.
Example 3:
Micro crystal isinglass active filler of aluminic acid ester surface modification (325 order) and preparation method thereof.The features such as the place of production, mineral composition, Chemical Composition and mineral physics of the microcrystal muscovite filler that this example adopted (325 order) are all identical with this patent example 1; Its Chemical Composition and physical and chemical performance are as shown in Table 1 and Table 2.
The aluminate coupling agent DL-411-D that this example adopted is identical with this patent example 1; Its surface modification technology is also identical with this patent example 1, as shown in table 3, this example coupling agent weight that different is is by microcrystal muscovite powder material: aluminic acid ester=100: 1.00, the aluminic acid ester amount ranges (wt%) of the used granularity microcrystal muscovite of this example powder is as shown in table 3.
This example adopts and example 1 same procedure, and surface modification effect is characterized and estimates, and shows that the coupling activation is respond well.
Example 4:
Micro crystal isinglass active filler of aluminic acid ester surface modification (800 order) and preparation method thereof.The features such as the place of production, mineral composition, Chemical Composition and mineral physics of the microcrystal muscovite filler that this example adopted (800 order) are all identical with this patent example 1; Its Chemical Composition and physical and chemical performance are as shown in Table 1 and Table 2.
The aluminate coupling agent DL-411-D that this example adopted is identical with this patent example 1; Its surface modification technology is also identical with this patent example 1, as shown in table 3, this example coupling agent weight that different is is by microcrystal muscovite powder material: aluminic acid ester=100: 1.50, the aluminic acid ester amount ranges (wt%) of the used granularity microcrystal muscovite of this example powder is as shown in table 3.
This example adopts and example 1 same procedure, and surface modification effect is characterized and estimates, and shows that the coupling activation is respond well.
Example 5:
Micro crystal isinglass active filler of aluminic acid ester surface modification (1250 order) and preparation method thereof.The features such as the place of production, mineral composition, Chemical Composition and mineral physics of the microcrystal muscovite filler that this example adopted (1250 order) are all identical with this patent example 1; Its Chemical Composition and physical and chemical performance are as shown in Table 1 and Table 2.
The aluminate coupling agent DL-411-D that this example adopted is identical with this patent example 1; Its table picture modified technique is also identical with this patent example 1, as shown in table 3, this example coupling agent weight that different is is by microcrystal muscovite powder material: aluminic acid ester=100: 2.80, the aluminic acid ester amount ranges (wt%) of the used granularity microcrystal muscovite of this example powder is as shown in table 3.
This example adopts and example 1 same procedure, and surface modification effect is characterized and estimates, and shows that the coupling activation is respond well.
Example 6:
Micro crystal isinglass active filler of aluminic acid ester surface modification (2500 order) and preparation method thereof.The features such as the place of production, mineral composition, Chemical Composition and mineral physics of the microcrystal muscovite filler that this example adopted (2500 order) are all identical with this patent example 1; Its Chemical Composition and physical and chemical performance are as shown in Table 1 and Table 2.
The aluminate coupling agent DL411-D that this example adopted is identical with this patent example 1; Its surface modification technology is also identical with this patent example 1, as shown in table 3, this example coupling agent weight that different is is by microcrystal muscovite powder material: aluminic acid ester=100: 3.90, the aluminic acid ester amount ranges (wt%) of the used granularity microcrystal muscovite of this example powder is as shown in table 3.
This example adopts and example 1 same procedure, and surface modification effect is characterized and estimates, and shows that the coupling activation is respond well.
Express one's thanks to:
This work is Sichuan Province's applied basic research fund (03JY029-026-1) and state natural sciences fund (40472028; 40272029) subsidize; Classmates such as Wang Yong, Li Wenjun, Yu Jinjiang also participate in part Study work, express thanks from the bottom of my heart in the lump at this.
Claims (3)
1, the preparation method of the active powder filler of a kind of microcrystal muscovite of aluminate coupling agent surface modification is a raw material with the microcrystal muscovite powder, it is characterized in that:
A, oven dry material are dried microcrystal muscovite powder material under 110 ℃ of conditions, remove whole adsorption moistures.It is definite that drying time should be done wet situation according to material, was generally 3 hours;
B, melting aluminum acid esters, for cured shape solid aluminium acid esters, should a little more than under 70～73 ℃ of its melting temperatures with the fusing of aluminic acid ester, solidify for preventing the aluminic acid ester, should under 70 ℃ temperature condition, preserve standby;
C, take by weighing material, take by weighing microcrystal muscovite powder oven dry material, and in the modified device temperature controllable high-speed mixer of packing into;
D, pre-thermal material make microcrystal muscovite powder material stir 30min in the high-speed mixer high speed, controlled temperature≤73 ℃;
E, high-speed mixing material slowly, are evenly poured the aluminic acid ester in the microcrystal muscovite powder material of high-speed mixer, high-speed mixing 20min, controlled temperature≤90 ℃.
2, the preparation method of the active powder filler of the microcrystal muscovite of a kind of aluminate coupling agent surface modification according to claim 1 is characterized in that:
Said aluminate coupling agent is meant at present the different trades mark produced by relevant enterprise and the aluminate coupling agent series product of title, and its chemical general formula is: (C
3H
7O) xAl (OCOR) m (OCORCOOR) n (OAB) y, wherein: x+m+n=3, y=0～2; R is a long-chain hydrocarbon, and carbon atom number is between 14～22; A, B are hydrocarbon short chain, and carbon atom number is between 6～8.
3, the preparation method of the active powder filler of the microcrystal muscovite of a kind of aluminate coupling agent surface modification according to claim 1 is characterized in that:
For varigrained aluminic acid ester surface modified micro crystal isinglass active filler series product, its aluminic acid ester DL-411-D consumption is respectively: when the granularity of microcrystal muscovite was 200 orders, the aluminic acid ester accounted for 0.50～0.55% of microcrystal muscovite weight; When the granularity of microcrystal muscovite was 325 orders, the aluminic acid ester accounted for 1.00～1.05% of microcrystal muscovite weight; When the granularity of microcrystal muscovite was 600 orders, the aluminic acid ester accounted for 1.20～1.25% of microcrystal muscovite weight; When the granularity of microcrystal muscovite was 800 orders, the aluminic acid ester accounted for 1.50～1.65% of microcrystal muscovite weight; When the granularity of microcrystal muscovite was 1250 orders, the aluminic acid ester accounted for 2.80～3.00% of microcrystal muscovite weight; When the granularity of microcrystal muscovite was 2500 orders, the aluminic acid ester accounted for 3.90～4.05% of microcrystal muscovite weight.
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| CN101613538B (en) * | 2009-07-22 | 2012-10-31 | 成都理工大学 | Method for surface modification of microcrystalline white mica powder with boric acid ester |
| CN102875981A (en) * | 2012-10-08 | 2013-01-16 | 合肥杰事杰新材料股份有限公司 | Micro-crystal muscovite/polybutylene terephthalate composite material |
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